Ether derivatives



Patented Feb. 7, 1950 ETHER DERIVATIVES Morris Katzman and Albert KrEpstein, Chicago,

Ill., assignors to The Emulsol Corporation, Chicago, 111., a corporation of Illinois No Drawing. Application January 11, 1945, Serial No. 572,422

1 Claim. 1

This invention relates to new chemical compounds which have particular utility in the arts where interface modifying functions are required.

One of the objects of the invention is the preparation of new chemical compounds having unusual resistance to decomposition in acid and alkali media.

Another object of the invention resides in the preparation of new chemical compounds which are particularly useful in enhancing the emulsification of oleaginous and aqueous materials.

' Other objects and features of the invention will become more apparent as the description proceeds.

In general, the compounds of the present invention may be characterized as ethers of alcohol amines in which the radical which unites with the alcohol amine or derivative thereof to produce the ether is a derivative of an aliphatic polyhydroxy substance in which at least one hydrogen of an hydroxy group is replaced by an organic radical containing at least six carbon atoms'and particularly from twelve to eighteen carbon atoms and in which another hydrogen of said aliphatic polyhydroxy substance is replaced by an aliphatic carboxylic acid radical containing up to five carbon atoms. In the preferred embodiments of the invention, the final ether compounds contain at least one free or unesterified hydroxyl group which is attached to the al- 001101 amine radical. The especially preferred compounds of the present invention are those which are derived from alcohol tertiary amines in which at least one of the hydroxy groups of the alcohol amine remains in free or unesterified form.

The ethers of thepresent invention may be prepared in various Ways. A particularly satis factory method of preparation involves the conversion of the alcohol amine into an alcoholate, for example, an alkali metal alcoholate, and then said alcoholate is reacted with a halide derivative of the derivative of the aliphatic polyhydroxy substance. The reaction results in the production of an alkali metal halogen salt Which may be separated from the reaction mixture in any de sired manner.

The following examples are illustrative of methods which may be employed for preparing the novel ether compounds of the present invention. As previously indicated, other methods may be used, the proportions of reacting ingredients, the times of reaction, the order of steps, and the temperatures may be varied and supplementary processes of purification and the like may be restored to wherever found desirable or convenient.

These and other variations and modifications will be evident to those skilled in the art in the light of the guiding principles which are disclosed here in.

Example I grams of commercial triethanolamine, 10 grams of metallic sodium in thin slices, and grams of a product consisting essentially of the mono-chloracetic acid mono-ester of coconut oil fatty alcohol mono-ethers of diethylene glycol are mixed together and allowed to stand at room temperature for one hour. 100 cc. of dry dioxane are then added and the mass is heated to refluxing temperature and allowed to reflux for at least two hours; ,It is then cooled and an excess of ether added thereto and the insoluble matter is then filtered off. The ether and dioxane are then evaporated under vacuum and the resulting product, a clear oil having good foaming properties, particularly in slightly acid media, contains a substantial proportion of a compound having the formula 50 grams of diethanolamine, 9 grams of meta1- lic sodium and grams of a product consisting essentially of a compound having the formula are reacted as described in Example I. The resulting product, possessing good foaming and wetting-out properties, comprises a compound having the formula OKs-( 2)1*O-Cz 2 4-)|- -C2 4-0-FC 2OC 14 v (L /NH v HO-CzHl Other examples of products which fall within the scope of the present invention and which may be prepared by methods generally similar to those described hereinabove are listed below:

(6) mN-oml-o-omi-o-oan-o-omn-o-cm-G While the'aboveexamples'representsingle substances; it,will'be understood that, in practice, it

maybe, in general, more advantageous to' employ mixtures of any two' or' more: thereof; with or without diluents, or reaction mixtures contain ing' said substances;

various compounds falling within the scope of the present invention will be produced.

Thesalcohol amines from which the ethers of amine; monoethyl diethanol'amin'e', monopro Y panolamine, dipropanolamine; tripropanolamine tri-isopropanolamine, dibutanoiamine; tributanolamine,. dipentanolamine, trihexanolaminaz N cyclohexyl dibutanolamine, diethanol aniline, monoethyl dipropanolamine, diethanol cyclohexylamine, monobutyl diethanolamine, diethanol methylamine, alkylol. primary: secondary and tertiary; amines of; other monoe orspolyvalenta ale cohols such as. glycols, glycerol, sugars: and. sugar: alcohols, such; as; sorbitolg. alkylol. polyaminea,

such, as alkylol derivatives of ethylenediamine, diethylene triamine and triethylene tetra-amine; arylol amines such as N-phenyl diethanoiamine and alkylolamines such as, for example,

Because of commercial and other considerations, it is preferred to employ the tertiary alkylol- Indeed; where commercial; sources of ingredients are utilized, mixtures'of' Among the compoundsmixtures of 4 amines, particularly, triethanolamine and triisopropanolamine.

The derivatives of the aliphatic polyhydroxy substances, the ethers with the alcohol amines of which comprise the novel compounds of the present; invention, are obtainable by; substituting alkyl (including cycloalkyl) radicals; of high molecular weight, in place of the hydrogen of one or more hydroxy groups of aliphatic polysubstances or polyhydric alcohols, it being understood that at least one hydroxy group attachedtothe nucleus of the polyhydroxy substance orpoly hydric alcohol remains. As examples'of suchderivatives may be mentioned partially:etherified;mono-, di-, and poly-saccharides,

andlsugar alcohols such as monolauryl ether of sucrose monostearyl ether of dextrose, monocetylether of sorbitol, monolauryl ether of pentaerythritol, monolauryhether of glycerol, monooleyl1ether; ofglycerol; monocetyl; ether: of: glycerol; di'cetyl ether of'gl'ycerol; monohexylr ether.- of glycerol,- monostearyl: etherof; glycerol monooctyl ether-of: diethylenerglycol,monolauryl ether of ethylene: glycol,. and the, like; The aiiphatic' polyhydroxy substancawhich: is partially etheri lied to provide one of the reacting constituents: hereinmay be selectedi from, a: lwge class and includes, among those, mentioned, glycerolz. ly- 001s such as ethylene: glycol; propylene, glycoL. trimethylene; glycol, butylene glycol :ami theslike; polyglycols-suchrasedirethylenerglycolttriethylene glycoL. tetraethylene gl col: andi, higher; hom0- logues; pentaerythritol; quercitol; dihydroxy, acetone;- polyglycerois such: as: diglycerol triglycerol; tetra lyceroland: the; likea including: tures thereof; carbohydrates and suga srinclude ingr mOnOe, difand: poly-sacoharidesi, such as: dextrose; sucrose, xylose; arabinosea. galactosew, fructose, maltosa. mannosa: dextrin; starch; antb the like; the: natural: and synthetic;, simple and; complex glucosides ;:sugar alcoholsgsuch as .arabh to mannitol, sorbitol and dulcitolt: anwhydroxw ethyl: and. hydroxy-propyl? etherderivatives oh the; above, as, forexample;

In, general, this, typa of. substance: may represented. by t-hediormulav wherein R is a radical containing at least six 76 and preferably from twelve to eighteen carbon te m atoms and selected from the group consisting of alkyl, cyclo-alkyl, aryl, and aralkyl, and substitution products thereof, A is the residue of the aliphatic polyhydroxy substance, and v and w are small whole numbers.

The aforesaid substances may be converted into halides, such as chlorine, bromine and iodine derivatives, and reacted with alkali metal alcoholates of the alcohol amines. 0r, alternatively, the aforesaid substances may be converted into alkali metal alcoholates and reacted with a halogen derivative of the alcohol amine. The compounds of the present invention have utility in various arts in which interface modifying agents are employed. They are particularly resistant to precipitation by calcium and magnesium salts and are especially compatible with acid and alkali media. They may be uti lized in washing, laundering and mercerizing baths in the textile and related industries wherein they function for softening, wetting, lathering, detergent, emulsifying, penetrating, dispersing, frothing and foaming purposes. The textiles, various treatments of which in the presence of the agents of the present invention are rendered effective, comprise natural products such as cotton, wool, linen and the like as well as the artificially produced fibres, (and fabrics) such as rayon, cellulose acetates, cellulose ethers and similar artificial silk fabrics. It will be understood, of course, that the agents may be used in aqueous and other media either alone or in combination with other suitable salts of organic or inorganic character or with other interface modifying agents. In the dyeing of textiles many of them may be employed as assistants in order to bring about even level shades. Many of them also may be used in the leather industry as wet ting agents in soaking, dyeing, tanning and the softening and other treating baths for hides and skins. Their utility as emulsifying agents enables them to be employed for the preparation of emulsions which may be used for insecticidal, fungicidal and for similar agriculture purposes. They have utility in the preparation of hair washes and hair shampoos, dentifrices of liquid, cream and powder type, cosmetic creams such as cold creams, vanishing creams, tissue creams, shaving creams of the brushless and lathering type and similar cosmetic preparations. Another use to which many of the agents may be placed is for the treatment of paper where they may be employed, for example, as penetrating agents in the cooking of the paper pulp or the like. Their capillary or interfacial tension. reducing properties enables them to be employed in the fruit and vegetable industry in order to effect the removal from fruits and the like of arsenical and similar sprays. They possess utility in the ore dressing industry wherein they function effectively in froth flotation and agglomeration processes. Their interface modifying properties also permit their use in lubrieating oils and the like enabling the production of effective boring oils, cutting oils, drilling oils, Wire drawing oils, extreme pressure lubricants and the like. They may also be used with effect in the preparation of metal and furniture polishes, shoe polishes, in rubber compositions, for breaking or demulsifying petroleum emulsions such as those of the water-in-oil type which are encountered in oil-field operations, and for various other purposes which will readily occur to those versed in the art in the light of the disclosure herein.

As detergents, they may in general be dissolved in water or aqueous media and utilized in that form or, in the case of solid products, they may be packaged and sold in such form preferably mixed with diluent/s. They may also be utilized for commercial cleansing, laundering and washing operations with advantage.

The products of the present invention may be employed alone or together with lesser or greater quantities of inorganic or organic compounds. Thus, for example, many of them may be employed together with salts such as sodium chloride, alkali metal phosphates including pyrophosphates and tetraphosphates, sodium sulphate, alums, perborates such as sodium perborate, and the like. They may be utilized in alkaline or :acid media in the presence of sodium carbonate, sodium bicarbonate, dilute acids such as hydrochloric, sulphurous, acetic and similar inorganic and organic acids. They may also be employed in the presence of such diverse substances as hydrophillic gums including pectin, tragacanth, karaya, locust bean, gelatin, arabic and the like, glue, vegetable, animal, fish and mineral oils, solvents such as carbon tetrachloride, monoethyl ether of ethylene glycol, monobutyl ether of ethylene glycol, monoethyl and monobutyl ethers of diethylene glycol, cyclohexanol, and the like. They may be used together with wetting, emulsifying, frothing, foaming, penetrating and detergent agents such aS the higher molecular weight alkyl sulphates, phosphates, pyrophosphates and tetraphosphates as, for example, lauryl sodium sulphate, myristy-l sodium pyrophosphate, cetyl sodium tetraphosphate, octyl sodium sulphate, oleyl sodium sulphate, and the like; higher molecular weight sulphonic acid derivatives such as cetyl sodium sulphonate and lauryl sodium sulphonate; sulphocarboxylic acid esters of higher molecular weight alcohols such as lauryl sodium sulphoacetate, dioctyl sodium sulphosuccinate, dilauryl potassium 'sulpho-glutarate, lauryl monoethanolamine sulpho-acetate, and the like; sulphuric and sulphonic derivatives of condensation products of alkylolamines and higher fatty acids; Turkey-Red oils; compounds of the type of isopropyl naphthalene sodium sulphonate, and other classes of wetting agents.

Many of the novel compounds of the present invention can be represented by the general formula (X alkylene-OH (RO).-A-O-(IJ JJH .,-0-alkylene--N N-Gi AOH This application is a continuation-in-part of our prior application, Serial No. 414,776, filed October 13, 1941, now Patent No. 2,390,942, issued December 11, 1945, which latter application is, in

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UNITED STATES" PATIENTS Numb Numbc Name Ham sa-w-iunr-w eb 9 Ka man 1m -v --r-.- J ly 28; 19 2 Kataman et'a l. Dec; 11,1945 FOREIGN PATENTS C unt y D t FrancQ-r -v-r-r-qq Nov. 12. 1938 

